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Патент USA US3073787

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3,073,777
er“
E
QC
. Patented Jan. 15.‘, 1953
2
'
3,073,777
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actor, it is advantageous to withdraw 0.1 to 2% by weight
(with reference to the initial‘ material) of an ash-con
.
PROCESS FOR THE DESTRUCTWE HYDREGGENA
0F CRUDE OHS, TARS AND THERE REFei
taining high boiling point oil.
in general the heat evolved by the hydrogenation reac
tion at this temperature is sufficient in order to achieve
the desired temperature rise. _It is also possible, how
‘ever, to supply additional heat to the reaction material,
for example by intermediate heating'up or by the addi
Willi Oettinger, Ludwigshafen (Rhine), Germany, assignor
to Badische Anilin- & Soda-Fabrik Aktiengeseilsehait,
Ludwigshafen (Rhine), Germany
'
,
'
No Drawing. Filed Feb. 17, 1960, Ser. No. 9,167
Claims priority, application Germany Feb. 19, 1959
4- Claims. (Cl. 208-59)
tion of hot gases at one or more places, or gases, as for
10 example carbon monoxide or oxygen, which will react
This invention relates to the destructive hydrogena—
tion of crude oils, tars and their residues.
It is known to subject crude oils, tars or their residues
to destructive hydrogenation by freeing the said initial
materials from inorganic constituents under pressure with
under the reaction conditions with the hydrogen with the
production of heat.
in general the pressure chosenin vthe pretreatment is
the same as is used in the subsequent hydrogenation. The
15 hydrogenating gas may be pure hydrogen, or a hydrogen
hydrogen at elevated temperature in a preliminary stage
in the presence of large-surfaced materials and then ef
fecting hydrogenation under. pressure in asecond stage.
I have now found that the inorganic constituents of
crude oils, tars or their residues can be removed in an
especially advantageous way by treating the said raw ma—
terials in the ?rst stage (preliminary stage) in the presence
containing gas, such as illuminating gas, town gas, water
, gas, cracking gas, coke oven gas or low temperature car
bonization gas.
.
>
As large-surfaced material there may be used porous
materials or non~porous materials, especially open hollow
bodies, as for example rings, hemispheres or angled struc
tures, such as cubes, cones, truncated cones, boxes, pyra
mids, which are open at leastion one side and which
of large-surfaced materials with a small amount of hy
drogen and then in a second stage in the presence of hy
drogenation catalysts with further amounts of hydrogen.
For example the procedure in industrial operation may
may contain de?ecting plates within the hollow space;
suitable materials are for example metallic substances, for
example metals of group VIII or stainless steel, or cer—
be that 0.1 to 0.5 normal cubic ‘meter of hydrogen or
hydrogen-containing gas per kilogram of initial material '
bleaching earths, aluminas or synthetically prepared sili
amic materials, such as porcelain, clay, cement, pumice,
cates. in many cases it has proved to be advantageous
or destructive hydrogenation is carried out in the second 30 to add to the large-surfaced material one or more sub
is used in the preliminary stage and thereafter the re?ning
stances having catalytic activity, such as molybdenum,
stage with at least 0.4 preferably 0.5 and advantageously
tungsten, chromium, vanadium, nickel, cobalt, platinum,
ruthenium, gold, manganese, titanium Or compoun'dsof
0.8, 0.9, 1.0 or more normal cubic meters of hydrogen
per kilogram of initial material. In many cases the use
of 1.5 normal cubic meters or more of hydrogen or hy
these or mixtures of the said elements or'their compounds.
‘it is of special advantage if the large-surfaced material
isarranged
in the reaction space in such, a' way that the
has proved advantageous. Throughout this speci?cation
material used ?lls the reaction space only to oneathird,
and in the appended claims, the expression “normal cubic
preferably‘ to the extent of at least40%v and advanta—
meters of hydrogen” is employed to de?nethe volume
of hydrogen as measured under standard conditions of 40 geously to the extent of about 50 to 70%§ ‘This maybe
achieved for example by using the said materials, as al
temperature and pressure, i.‘e. at 0° C. and 760 mm. Hg.
ready mentioned,v in the form of suitable rings or other
An advantageous embodiment of the process comprises
voluminous open or partly closed structures offering large
leading the‘ initial material through the preliminary stage
surfaces.
‘
with only the hydrogen which is freshly supplied to the
The chamber for the large-surfaced materials is in gen~ '
system, the Whole of the hydrogen which is being circu
drogen-containing gas per kilogram of initial material
lated then being added prior to the second stage.
eral smaller than. the actual reaction chamber which is
'
provided with the hydrogenation catalyst and in which
the cracking, re?ning and/ or aromatizing pressure hy
The process according to this invention is suitable for
all kinds of pressure hydrogenation, for example for the
drogenation takes place, advantageously in a plurality of '
re?ning, cracking and/or aromatizing hydrogenation in
stages, at pressures of 5 to 700 atmospheres, especially
20 to 300 atmospheres, and at "temperatures of 350° to
which high boiling point initial materials, such as crude
oils, tars, shale oils or their residues which boil above
550° C., preferably with rising temperature. The
300° C., as for example distillation, extraction or crack
_
throughput may ‘be chosen between 0.3 and 10 kilograms
ing residues, are worked up.
of initial material per'part by volume of catalyst per hour.
The said initial materials are heatedto at least 250° C.,
The circulating gas containing hydrogen may be washed
advantageously to at least 300° C., for example to a tem 55
with an extraneous oil or with an oil originating from
perature between 310° and 350° C. and then led into a
the process, for example with a heavy gasoline or a gas
reaction chamber provided with large-surfaced material.
oil. To remove ammonia, the gas may be treated with
This reaction chamber may consist of a single vessel or
water or an acid solution, possibly in association withan
a plurality of consecutive vessels. In this reaction cham—
her the temperature is gradually increased, for example 60 oil washing. The washing may take place in co- or
counter-current, preferably under the reaction pressure.
to 370° C., 400° C. or more. The distribution of tem
As catalysts for the treatment there may be used those
perature when using two vessels may be for example: in _
having hydrogenating, cracking, dehydrogenating, isomer—
the ?rst vessel a rising temperature is chosen within the
izing and/or cyclizing properties, as for example oxides,
range of about 280° to 360° C. and in the second vessel
sul?des, selenides, tellurides, sulfates, borates, nitrates,
a rising temperature between about 360° C. and the re
action temperature. This method ensures a satisfactory
carbonates, halides, phosphorus compounds or also silii
cates of vanadium, molybdenum, tungsten, chromium,
removal of ash Without separation of coke taking place.
It is however possible to apply increasing temperatures
only in the second vessel, while in the ?rst vessel a sta
tionary or even slightly falling temperature is maintained.
After the ?rst reactor, and in the case of several con
secutive reactors preferably after the second or last re
uranium, rhenium, iron, nickel, or cobalt, and’ also- gold,‘
'
silver, copper, tin, titanium lead, zinc, magnesium, 'cadii
70
mium, zirconium, antimony, bismuth and manganese, and, '
also the metals of the platinum, palladium and iron" groups,
' and the heavy metals of group I or mixtures thereof.
._ ‘
' "
3,073,777
for example the said compounds of molybdenum, tung
sten, chromium and vanadium may be used in admixture
or in chemical combination, for example as molybdates,
4
The following example will further illustrate this inven—
tion but the invention is not restricted to this example.
Example
tungstates, chromates, chromites, vanadates, or titanates,
with compounds of nickel, cobalt, titanium, tin or lead 5
A distillation residue boiling above 370° C. and con
and/or with the metals of the platinum and palladium
taining 4.2% of sulfur which has been obtained from
group and/or heavy metals of group I and'their com
pounds, the added substances preferably being used in
Near Eastern crude oil is heated up to 340° C. under a
pressure of 200 atmospheres together with 0.3 normal
smaller amounts than molybdenum, tungsten, chromium
cubic meter of hydrogen per kilogram of oil and lead into
and vanadium. Molybdenum or tungsten with cobalt, 10 a ?rst reactor (preliminary vessel 1) which is ?lled with
nickel and/or titanium and possibly tungsten or molyb
Raschig rings of clay which have been impregnated with
denum, for example, are especially suitable. Some ele
3.5% by weight of M003. There is a free space of 70%
ments have proved to be promoters for the more usual
catalysts of groups V to VIII of the periodic system, as
for example gold, silver, mercury, titanium, copper, zinc,
tin or uranium and lead or compounds thereof. Mixtures
are also suitable which consist of compounds of the said
by volume in the preliminary vessel I. The throughput
amounts to 1.7 kilograms of oil per liter of Raschig rings
per hour and the temperature at the outlet from this pre
liminary vessel I is 375° C.
After leaving the preliminary vessel I, the gas-oil mix
metals of group IV of the periodic system, for example
ture is further heated to 400° C. and led into a second re
titanium with compounds of iron, nickel, cobalt or man
actor (preliminary vessel II) which is provided with Ras
ganese, as well. as of copper, silver, gold, platinum, pal 20 chig rings of the same composition and with the same
ladium, ruthenium or their compounds or in chemical com
degree of ?lling. The throughput with reference to the
bination as titanates. Compounds of the metals of the iron
preliminary vessel H is 2.0 kilograms of oil per liter of
group in admixture with platinum, palladium, ruthenium,
Raschig rings per hour and the temperature at the outlet
copper, silver, gold or their compounds are also suitable.
therefrom is maintained at 430° C.
These mixtures may also be used in the form of chemical 25
The mixture of gas and oil then passes, with the addi
compounds. Since compounds of the alkali and alkaline
tion of circulating gas which has been heated up to the
earth metals in?uence the activity of the catalysts, their
same temperature, into a third reactor which is ?lled with
activity may be adjusted by their use. The said catalysts
rigidly arranged catalyst. The catalyst consists of active
may be applied in an amount of 0.1 to 30% by weight to
alumina with 5% of silicic acid and 3% of titanium oxide
‘carriers in moist or calcined condition. Suitable carriers 30 which has been provided with cobalt and molybdenum
are acid-treated montmorillonite, active silica, silica gel,
oxides in such amount that the ?nished catalyst contains
preferably together with the oxides of titanium, thorium,
2% by weight of cobalt and 12% by weight of molyb
zirconium and magnesium, titania gel or titanium oxide,
denum (calculated as metal). The catalyst has a cylindri
optionally together with 0.1 to 30% by weight of SiOz
cal shape having a diameter of 7 mm. and about the same
as silicates, bleaching earth, fuller’s earths, synthetic sili 35 height. The temperature is maintained at 440° C. The
cates, for example aluminum and/or magnesium silicates,
throughput, with reference to this third reactor, is 0.6
and also the above-mentioned silicates, active aluminas,
kilogram per liter of catalyst per hour. In this third re
preferably with a surface of more than 300 square meters
per gram, aluminum hydroxide or peptized aluminas,
actor, in which desulfurization takes place, a gas to oil
ratio of 1.1 normal cubic meters of gas to 1 kilogram of
which have been treated with an amount of an acid in 40 oil is maintained.
su?icient to effect complete dissolution, bauxite, optional
The reactants then pass through a condenser into a
ly with 0.1 to 25% by weight SiOg, titanium oxide, zir
conium oxide, cerium oxide, zinc oxide and/or magnesium
oxide. When using synthetically prepared carriers, such
as silica, silicates, aluminas or titanium oxide, the com
separator in which the gas is separated from the liquid.
The liquid reaction product contains 0.8% by weight of
sulfur. The gas is circulated to the third reactor.
In order to maintain the highest possible hydrogen
ponent with catalytic activity may be added during the
production, for example by adding a soluble compound
of the catalytically acting metal to the waterglass solution,
partial pressure and to avoid corrosion, the hydrogen sul
dibasic acid, suitable acids being hydrogen chloride, hy
and II.
?de partial pressure is kept below 1 atmosphere by wash~
ing the circulating gas.
to the silica sol, the titanium salt solution, the aluminum
After an operating period of three months, the system
salt and/or aluminate solution, and then precipitating the 50 is closed down. In the preliminary vessels I and II 94%
solution and/or the metal or metal compound during the
of the inorganic constituents introduced with the crude
precipitation. It is advantageous to treat the carrier with
oil are found.
gases, such as ammonia, hydrogen, sulfur dioxide, halo
If a gas to oil ratio of 1.1 normal cubic meters of gas
gen or rare gases, and the gas may remain in the pores.
to 1 kilogram of oil is maintained in all three reactors,
The carrier may also be pretreated with hydrogen halide
only about 65% of the inorganic constituents introduced
or an inorganic or low molecular organic monobasic or
with the crude oil are found in the preliminary vessels I
'
drogen ?uoride, chlorosulfonic acid, formic acid or oxalic
What I claim is:
acid. The carrier may take up halogen in an amount of
1. In a process for the re?ning and destructive hy
0.1 to 10% by weight. The catalyst may also be molded 60 drogenation of crude oils, tars and their residues as ini~
with carbon and the carbon then wholly or partly re
tial material by reaction with hydrogen in a ?rst stage
moved by calcining.
When working under pressures up to about 150 atmos
containing large-surfaced materials and by further reac
tion with hydrogen in a second stage in the presence of a
pheres, the catalyst is in general reactivated from time to
hydrogenation catalyst and at a temperature of 350° C. ,
time with oxygen or a gas containing oxygen at tempera 65 to 550° C., the pressure in both stages being in a range of
tures of 450° to 600° C. The catalyst or the catalyst car~
about 5 to 700 atmospheres, the improvement which com
rier or both may also be exposed prior to use to a tem
prises: heating said initial material to a temperature be
perature above 300° C., for example 400° to 600° C., for
tween about 250° C. and 350° C.; then leading said ini
tial material through said ?rst stage together with about
70
The catalysts may be arranged rigidly in the reactor in
0.1 to 0.5 normal cubic meters of hydrogen per kilogram
known manner or ‘they may be present in the reactor in
of initial material and subsequently through said second
a moving condition. The initial material may be led over
stage together with about 0.5 to 1.5 normal cubic meters
the catalyst with hydrogen in concurrent or countercur
of hydrogen per kilogram of initial material.
l a prolonged period.
rent flow.
'
2. A process as claimed in claim 1 wherein the tem
3,073,777
.
perature in said ?rst stage is gradually increased from
said temperature between 250° C. and 350° C. up to not
more than the reaction temperature in said second stage.
3. A process as claimed in claim 1 wherein the pres-
_
I
5
4. A process as claimed in claim 3 wherein the pres~
sure is approximately equal in both stages.
References Cited in the ?le Of this Patent
sure in both stages falls in a range of about 20 to 300 5
UNITED STATES PATENTS
atmospheres and the initial
to
A
smaterial is heated
o
a a tem-_
2,098,400
.
'
Pier
et a1. ___________
__ Nov. 9, 1937
perature between about 300 C. and 350
2,706,705
Oettinger et a1 ________ __ Apr‘ 19, 1955
ing led through said ?rst stage.
C. before he
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